Benzyl Alcohol → Benzyl cyclopent-3-en-1-ylcarbamate

HRID 609544Notes

Reaction equation

HRID 609544 reaction equation
[CH:1]1(C(O)=O)[CH2:5][CH:4]=[CH:3][CH2:2]1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:16])C=CC=CC=1.C([N:28]([CH2:31]C)CC)C.[CH2:33]([OH:40])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>C1C=CC=CC=1>[CH:1]1([NH:28][C:31](=[O:16])[O:40][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[CH2:2][CH:3]=[CH:4][CH2:5]1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 8537563-Cyclopentene-1-carboxylic acid

Product 1

HCID 10751243Benzyl cyclopent-3-en-1-ylcarbamate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

A solution of 3-cyclopentene-1-carboxylic acid (Depres and Greene, J. Org. Chem. 1962, 27:2395-2398) (30.5 g, 0.272 mole) in dry benzene (360 mL) was stirred while a solution of diphenylphosphoryl azide (Aldrich, 74.85 g, 0.272 mole as 97%) and triethylamine (41.7 mL, 0.299 mole) in benzene (130 mL) was added over 20 minutes. The solution was refluxed for 2 hours and then benzyl alcohol (32.4 mL, 0.313 mole) was added. The solution was refluxed for 20 hours, cooled, and concentrated in vacuo to a brown oil. A solution of the oil in ethyl acetate (600 mL) was washed with 0.5 N hydrochloric acid (300 mL), then water (2×350 mL), then saturated aqueous sodium bicarbonate (300 mL), and dried (sodium sulfate). Evaporation left title compound as white solid (41.0 g, 69%), 1H-NMR consistent with structure. Recrystallization of such a sample from ethyl acetate-hexanes gave benzyl N-(3-cyclopenten-1-yl)carbamate as colorless waxy crystals, m.p. 56-57° C.

Workup

  1. additionwas added over 20 minutes
  2. temperatureThe solution was refluxed for 2 hours
  3. temperatureThe solution was refluxed for 20 hours
  4. temperaturecooled
  5. concentrationconcentrated in vacuo to a brown oil
  6. washA solution of the oil in ethyl acetate (600 mL) was washed with 0.5 N hydrochloric acid (300 mL)
  7. dry with materialwater (2×350 mL), then saturated aqueous sodium bicarbonate (300 mL), and dried (sodium sulfate)
  8. customEvaporation
  9. waitleft title compound as white solid (41.0 g, 69%)
  10. customRecrystallization of such a sample from ethyl acetate-hexanes

Sources & evidence

ORD record
ord-a33b5a2db10d40d08e780360c6e83bf6
Source dataset
uspto-grants-1999_12
Patent number
US05998398

Reaction notes

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